KR20080014015A - Flame retardant composition exhibiting superior thermal stability and flame retarding properties and use thereof - Google Patents

Abstract

The present invention relates to a flame retardant composition exhibiting superior thermal stability and flame retarding properties and its use thereof.

Description

Flame retardant compositions exhibiting excellent thermal stability and flame retardant properties and their use {FLAME RETARDANT COMPOSITION EXHIBITING SUPERIOR THERMAL STABILITY AND FLAME RETARDING PROPERTIES AND USE THEREOF}

Reference to related application

This application is directed to US Provisional Patent Application No. 1, filed June 7, 2005. United States Provisional Patent Application No. 60 / 688,385 and filed June 7, 2005. Priority is given to 60 / 688,467, the disclosures of which are hereby incorporated by reference in their entirety.

The present invention relates to a flame retardant composition exhibiting excellent thermal stability and flame retardant properties. More specifically, the present invention relates to flame retardant compositions and uses thereof; The flame retardant composition contains N-2, CASE (F1) -74623-dibromopropyl-4,5-dibromohexa hydrophthalimide and a flame retardant and thermal stability improver.

The effectiveness of flame retardant compounds is typically due to two important properties i) flame retardancy and ii) thermal stability. The flame retardancy of the flame retardant compound is typically determined according to its Limiting Oxygen Index (“LOI”), which is generally measured according to ASTM D2863. The LOI value provides the oxygen concentration of the oxygen / nitrogen mixture that only sustains combustion of the material, and the higher the LOI value, the better the flame retardant ability of the compound.

Thermal stability is typically measured by thermogravimetric ("TGA") analysis. This analysis involves increasing the polymer temperature in 10 or 20 ° C. increments and measuring the temperature at which the flame retardant loses a set weight percentage, ie, 5 wt%, 10 wt%, and the like. The TGA test is a comparative test, that is, a flame retardant compound that is hotter at a weight loss level compared to another flame retardant compound at the same weight loss level is said to have better thermal stability than a lower flame retardant compound.

In general, there is an increasing demand in the polymer industry for flame retardant compounds having superior thermal stability properties compared to those currently available which impart flame retardancy to styrenic polymers containing flame retardant compounds as well. Therefore, there is a need in the art for flame retardants having this feature.

The figure is a graph comparing the limiting oxygen index ("LOI"), ie flame retardant efficiency, of flame retardant polymer formulations according to the invention.

Summary of the Invention

The present invention relates to a flame retardant composition having enhanced thermal stability and flame retardant efficiency in extruded polystyrene foam, the composition comprising:

a) about 60% to about 95% by weight of N-2,3-dibromopropyl-4,5-dibromohexahydrophthalimide based on the flame retardant composition;

b) about 1% to about 40% by weight based on the flame retardant composition, i) natural zeolite, ii) synthetic zeolite, iii) halogenated aromatic epoxide, iv) halogenated epoxy oligomer, v) non-halogenated epoxy oligomer, vi ) Component (A) selected from a hydrotalcite and a mixture of vii) i) -vi); And

Randomly

c) (i) antimony compounds; (ii) tin compounds; (iii) molybdenum compounds; (iv) zirconium compounds; (v) boron compounds; (vi) hydrotalcites; (vi) talc; (vii) dicumylperoxide; (viii) dicumyl; (ix) hindered phenolic antioxidants; (x) light stabilizers; And xi) a synergist selected from a mixture of i) -x ).

The invention also relates to a polystyrene formulation comprising a flame retardant amount of a flame retardant composition according to the invention.

The invention also relates to an extruded polystyrene foam containing the flame retardant amount of the flame retardant composition according to the invention.

The invention also relates to articles made from such flame retardant extruded polystyrene foams.

The invention also relates to a process for the production of shaped flame retardant extruded polystyrene products comprising blending a blowing agent and a flame retardant composition according to the invention to form a blended product and extruding the blended product through a die. .

Detailed description of the invention

The present invention, collectively referred to herein as "flame retardant I", in the range of about 60% to about 95% by weight, preferably in the range of about 90% to about 95% by weight of N-2,3-di A flame retardant composition comprising bromopropyl-4,5-dibromohexahydrophthalimide, tautomeric forms thereof, stereoisomers, and polymorphs:

.

.

Flame retardant I exhibits very good solubility in polystyrene. Flame retardant I has solubility in polystyrene at 20 ° C. in the range of about 0.5 to about 8% by weight based on the weight of polystyrene and flame retardant I, and in the range of about 0.5 to about 10% by weight at 40 ° C. on the same basis. Flame retardant I also has no detrimental effect on the formation of polystyrene foam, which, when added with the solubility of flame retardant I, makes flame retardant I more suitable for use in polystyrene foams than most other flame retardants.

Flame retardant compositions of the present invention may also be used in the range from about 1% to about 40% by weight, i) natural zeolites, ii) synthetic zeolites, iii) halogenated aromatic epoxides, iv) halogenated epoxy oligomers, v) non-halogenated epoxy oligomers, vi) hydrotalcite, and vii) component (A) selected from the mixture of i) -vii). Component A is a substance that provides a dual function in the present invention. First, it acts as a heat stabilizer for N-2,3-dibromopropyl-4,5-dibromohexahydrophthalimide containing flame retardant compositions. Secondly, it also provides additional flame retardant efficacy to the flame retardant composition. Component A is preferably at least one of hydrotalcites, halogenated aromatic epoxides, halogenated epoxy oligomers, non-halogenated epoxy oligomers. More preferably component A is at least one of halogenated aromatic epoxides, halogenated epoxy oligomers, non-halogenated epoxy oligomers. In a more preferred embodiment, component A is selected from halogenated aromatic epoxides, halogenated epoxy oligomers, and mixtures thereof. In the most preferred embodiment, component A is a hydrotalcite.

Component A is preferably present in an amount ranging from about 1 to about 25 weight percent based on flame retardant I. In another preferred embodiment, component A is present in an amount ranging from about 1 to about 15 weight percent, more preferably from about 3 to about 12 weight percent, based on flame retardant I.

Zeolite

Natural zeolites suitable for use herein may be selected from any known natural zeolites. Synthetic zeolites suitable for use herein can be selected from any known synthetic zeolites. Preferably the synthetic zeolites are selected from Zeoline, available from Praeon, or Zeolite A, available under the trade name EZA from Albemarle Corporation. Zeolite A used in the practice of the present invention is a generalized formula for zeolites M _{2 / n} OAl ₂ O ₃ ySiO ₂ wH ₂ O (wherein M is an IA or IIA group element such as sodium, potassium, magnesium and calcium) ) For a sodium zeolite, the formula is _{Na 2 OAl 2 O 3 xSiO 2} wH 2 O ( wherein, x value usually is in the range of 1.85 ± 0.5, values for y can vary, any of about 6 or less May be the value of). On average, the y value will be about 5.1. For sodium Zeolite A, the formula may be represented as 1.0 ± 0.2Na ₂ OAlO ₃ 1.85 ± 0.5SiO ₂ yH ₂ O (where the y value may be about 6 or less). Ideal Zeolite A has the formula (NaAlSiO ₄ ) ₁₂ 27H ₂ O.

Halogenated aromatic epoxides

Halogenated aromatic epoxides suitable for use in the present invention are preferably diglycidyl ethers of halogenated bisphenol-A, wherein about 2 to about 4 halogen atoms are substituted on the bisphenol-A moiety and halogen atoms are chlorine and / or It's bromine. More preferably, the halogen atoms on the bisphenol-A moiety are substantially all bromine atoms. Most preferably, the halogenated aromatic epoxides are brominated epoxy resins prepared from TBBPA and epichlorohydran, the Praetherm ^™ series sold by Dainippon Ink & Chemicals, preferably EP-16, and commercially available from Resolution Performance Products. It is selected from "EPIKOTE Resin-5203".

Halogenated aromatic epoxy oligomers

Halogenated aromatic epoxy oligomers suitable for use herein are halogenated bisphenol-A type epoxy resins represented by formula (I):

[Wherein X represents a halogen atom; i and j each represent an integer of 1 to 4; n represents an average degree of polymerization in the range from 0.01 to 100, typically in the range from 0.5 to 100, preferably in the range from 0.5 to 50, and more preferably in the range from 0.5 to 1.5; And T ₁ and T ₂ are independently and preferably as follows:

{Wherein Ph represents a substituted or unsubstituted halogenated phenyl group, wherein the ring is substituted with one or more chlorine or bromine atoms}]. Non-limiting examples of Ph include single or mixed isomers of bromophenyl, single or mixed isomers of dibromophenyl, single or mixed isomers of tribromophenyl, single or mixed isomers of tetrabromophenyl, pentabromophenyl , Single or mixed isomers of chlorophenyl, single or mixed isomers of dichlorophenyl, single or mixed isomers of trichlorophenyl, single or mixed isomers of tetrachlorophenyl, pentachlorophenyl, tolyl groups in which the ring is substituted with two bromine atoms Single or mixed isomers, single or mixed isomers of tolyl groups in which the ring is substituted with two chlorine atoms, and single or mixed isomers of ethylphenyl group in which the ring is substituted by two bromine atoms. Each halogen atom in the Ph group is preferably a bromine atom. As will be shown below, end-blocking groups other than Ph may be used.

Halogenated aromatic epoxy oligomers suitable for use herein are typically amorphous oligomeric materials having an epoxy equivalent of greater than 500 g / eq, and preferably greater than 800 g / eq. Thus, U.S. for use in stabilization of hexabromocyclododecane. Patent No. Unlike the crystalline diglycidyl ethers of tetrabromobisphenol-A having an epoxy equivalent of 320 to 380 g / eq described in 6,127,558, the halogenated aromatic epoxy oligomers used in the practice of the present invention are not specifically processed to achieve a crystalline structure. If not very effective it is not characterized by this very low epoxy equivalent.

Non-limiting examples of one group of brominated bisphenol-A epoxy oligomers suitable for use herein are those compounds represented by the following general formula (II):

[Wherein n represents an average degree of polymerization which is in the range of 0.5 to 100, typically in the range of 0.5 to 50, and preferably in the range of 0.5 to 1.5].

Non-limiting examples of commercially available products represented by the formula (II) include Bromokem (Far East) Ltd. "F-2300", "F-2300H", "F-2400" and "F-2400H" manufactured by Dainippon Ink & Chemicals, Incorporated "PRATHERM EP-16", "PRATHERM EP-30", "PRATHERM EP-" 100 "and" PRATHERM EP-500 ", Sakamoto Yakuhin Kogyo Co., Ltd. "SR-T1000", "SR-T2000", "SR-T5000" and "SR-T20000" manufactured by Corporation, and "EPIKOTE Resin-5112" manufactured by Resolution Performance Products.

Brominated bisphenol-A epoxy oligomers in which epoxy groups at each end of the resin are blocked with a blocking agent, and resins in which only epoxy groups at one end are blocked with a blocking agent are also suitable for use herein as halogenated aromatic epoxy oligomers. Non-limiting examples of suitable blocking agents include those blocking agents that allow the ring-opening addition of epoxy groups, such as phenols, alcohols, carboxylic acids, amines, isocyanates, etc., each containing bromine atoms. Among them, brominated phenol is preferable for improving the flame retardant effect. Examples thereof may include dibromophenol, tribromophenol, pentabromophenol, dibromoethylphenol, dibromopropylphenol, dibromobutylphenol, dibromocresol and the like.

Examples of brominated bisphenol-A epoxy oligomers in which the epoxy groups at both ends thereof are blocked with a blocking agent can be represented by the following formulas (III) and (IV):

[Wherein n represents an average degree of polymerization in the range of 0.5 to 100, typically in the range of 0.5 to 50, and preferably in the range of 0.5 to 1.5].

Non-limiting examples of commercially available products of formula (III) or (IV) include "PRATHERM EC-14", "PRATHERM EC-20" and "PRATHERM EC-30", manufactured by Dainippon Ink & Chemicals, Incorporated, Tohto Chemical Co., Ltd. "TB-60" and "TB-62" manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. "SR-T3040" and "SR-T7040" manufactured by "PIC" and "EPIKOTE Resin-5203" manufactured by Resolution Performance Products.

Brominated bisphenol-A epoxy oligomers in which the polymer has a blocking agent at one end can be represented by the following formulas (V) and (VI):

[Wherein n represents an average degree of polymerization in the range of 0.5 to 100, typically in the range of 0.5 to 50, and preferably in the range of 0.5 to 1.5].

Non-limiting examples of commercially available products of formula (V) or (VI) include "PRATHERM EPC-15F" from Dainippon Ink & Chemicals, Incorporated, and "E5354" from Yuka Shell Epoxy Kabushiki Kaisha.

Non-halogenated aromatic epoxy oligomers

Non-halogenated epoxy oligomers suitable for use herein may take the form of any of those having formulas (I)-(VI) above. However, in non-halogenated epoxy oligomers, the halogen component is replaced with a hydrogen atom. For example, bisphenol-A epoxy oligomers are suitable for use herein as non-halogenated epoxy oligomers. Non-limiting examples of non-halogenated epoxy oligomers suitable for use herein include any available epoxy resin made from bisphenol A and epichlorohydrin.

Hydrotalcite

Hydrotalsheets suitable for use herein include both natural and synthetic hydrotalsheets. In general, hydrotalsheets suitable for use in the present invention include those represented by the following general formula:

M ²⁺ _1-x M ³⁺ (OH) ₂ (A ^n- ) _{x / n} mH ₂ O

[ ^Wherein M ²⁺ is selected from the group consisting of Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Zn ²⁺ , Cd ²⁺ , Pb ²⁺ , Sn ²⁺ , or Ni ²⁺ ; ; And M ³⁺ is Al ³⁺ , B ³⁺ ; Or Bi ³⁺ ; A ^n- is preferably ^{OH -, Cl -, Br -} , I -, ClO 4 -, HCO 3 -, CH 3 COO -, C 6 H 5 COO -, CO 3 -2, SO 4 -2, ( _{^{COO -) 2, (CHOH)}} 4 CH 2 OHCOO -, C 2 H 4 (COO) 2 -2, (CH 2 COO) 2 -2, CH 3 CHOHCO -, SiO 3 -2, SiO 4 -4, Fe ^{_{(CN) 6 -3, Fe (}} CN) 6 -4 or HPO ₄ ^-2, selected from the group consisting of an anion having a valence of n; n is a number ranging from about 1 to about 4; x is a number ranging from about 0 to about 0.5; m is a number ranging from about 0 to about 2; Preferably, M ²⁺ is Mg ²⁺ or a solid solution of Mg and Zn, M ³⁺ is Al ³⁺ ; A ^n- is CO ₃ ^-2 or SO ₄ ^-2 , x is a number ranging from 0 to 0.5, and m is a positive value.

Exemplary hydrotalcites include Al ₂ O ₃ .6MgO.CO ₂ .12H ₂ O; Mg _4.5 Al ₂ (OH) _13. CO ₃ .3.5H ₂ O; 4MgO.Al ₂ O ₃ .CO ₂ .9H ₂ O; 4MgO.Al ₂ O ₃ .CO ₂ .6H ₂ O; ZnO ₃ MgO.Al ₂ O ₃ .CO ₂ .wH ₂ O (where w is in the range 8-9), and ZnO.3MgO.Al ₂ O ₃ .CO ₂ .wH ₂ O (wherein Is in the range 5-6), but is not necessarily limited thereto.

Some experimental formulas of some preferred hydrotalcites, provided by commercial suppliers, include Mg _4.5 Al ₂ (OH) ₁₃ .CO ₃ , Mg _4.5 Al ₂ (OH) ₁₃ .CO ₃ .3H ₂ O, Mg _4.5 Al ₂ (OH) ₁₃ .CO ₃ .3.5H ₂ O, and Mg _4.5 Al ₂ (OH) ₁₃ .0 _0.2 . (CO ₃ ) _0.8 .

Hydrotalcites having the above general formula are readily available commercially. Some common suppliers of such hydrotalsheets include Kyowa Chemical Industry Co., Ltd., which supplies hydrotalcite under the trade names ALCAMIZER, DHT-4A, DHT-4C and DHT-4V; And J. M. Huber Corporation, which supplies hydrotalcites under the trade names Hysafe 539 and Hysafe 530. In a particularly preferred embodiment of the invention, the hydrotalcite used herein is available from Kyowa Chemical Industry Co., Ltd, with DHT-4A hydrotalcite being particularly preferred.

As mentioned above, in a preferred embodiment, component A is a hydrotalcite. In this embodiment, the hydrotalcite is present in an amount ranging from about 1 to about 25 weight percent based on the weight of the flame retardant composition. Preferably, the hydrotalcite is present in an amount ranging from about 1 to about 15 weight percent on the same basis, and more preferably the hydrotalcite ranges from about 1 to about 10 weight percent on the same basis, most preferably about It is present in an amount ranging from 2 to about 6 weight percent.

Extruded polystyrene foam

In another embodiment, the present invention is a flame retardant polymer formulation comprising more than about 50% by weight of extruded polystyrene foam based on the weight of the flame retardant polymer formulation and the flame retardant amount of the flame retardant composition according to the present invention. Preferably the flame retardant polymer comprises more than about 75% by weight of extruded polystyrene based on the weight of the flame retardant polymer formulation, and more preferably from about 90% to about 99.5% by weight of extruded polystyrene foam on the same basis.

The flame retardant compositions of the present invention are particularly suitable for use in extruded polystyrene foam. Non-limiting examples of the use of such foams include thermal insulation. Extruded polystyrene foams suitable for use herein can be prepared by any process known in the art, one of which methods includes forming expanded polystyrene foams from vinyl aromatic monomers having the formula:

H ₂ C = CR-Ar;

[Wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms and Ar is an aromatic group having about 6 to about 10 carbon atoms (including various alkyl and halo ring-substituted aromatic units), for example, a styrene-based polymer]. Non-limiting examples of such vinyl aromatic monomers include styrene, alpha-methylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, para-ethylstyrene, isopropylpenttoluene, isopropylnaphthalene, vinyl toluene, vinyl Naphthalene, vinyl biphenyl, vinyl anthracene, dimethylstyrene, t-butylstyrene, some chlorostyrenes (such as mono- and di-chloro variants), and some bromostyrenes (such as mono-, dibromo- and tribromo Variants) are included. Non-limiting examples of the use of such foams include thermal insulation.

According to one aspect of the invention, the monomer is styrene. Polystyrene is readily prepared by bulk or lumps, solutions, suspensions, or emulsion polymerization techniques known in the art. Polymerization can be affected in the presence of free radical cationic or anionic initiators. Non-limiting examples of suitable initiators include di-t-butyl peroxide, azeo-bis (isobutyronitrile), di-benzoyl peroxide, t-butyl perbenzoate, dicumyl peroxide, potassium persulfate, aluminum Trichloride, boron trifluoride, etherate complex, titanium tetrachloride, n-butyllithium, t-butyllithium, cumyl potassium, 1,3-tririthiocyclohexane and the like. Additional details regarding the polymerization of styrene alone or in the presence of one or more monomers copolymerizable with styrene are well known in the art.

Polystyrenes used in the present invention typically have a molecular weight of at least about 1,000. In some embodiments, the polystyrene has a molecular weight of at least about 50,000. In other embodiments, the polystyrene has a molecular weight ranging from about 150,000 to about 500,000. However, it should be noted that, where appropriate or necessary, polystyrenes having higher molecular weights can be used.

Flame Retardant Composition

As mentioned above, the flame retardant polymer formulation of the present invention comprises the amount of flame retardant of the flame retardant composition according to the present invention. Flame retardant generally refers to a test specimen capable of achieving a DIN 4102 test of B2 or greater or a UL 94 test grade of V-2 or greater with a 1 / 8-inch thickness for specimens 10 mm thick (for EPS and XPS). Means sufficient amount to provide. In most cases, the flame retardant amount will be an amount sufficient to provide a total halogen content in the range of about 0.3 to about 10 weight percent, and preferably in the range of about 0.5 to about 6 weight percent, based on the weight of the flame retardant polymer formulation. . Generally, this amount is in the range of about 0.01% to about 50% by weight, preferably in the range of about 0.01% to about 25% by weight, and more preferably on the same basis, based on the weight of the flame retardant polymer formulation. In the range from about 0.5% to about 7% by weight. In the most preferred embodiment, the flame retardant amount is in the range of about 1% to about 5% by weight of the flame retardant composition on the same basis. However, in some embodiments, the amount of flame retardant is a flame retardant composition in the range of about 3% to about 4% by weight on the same basis.

Flame Retardant Polymer Formulations

The flame retardant polymer formulations of the present invention may be formed by any known process or method. Exemplary procedures include melting the polystyrene resin in the extruder. The molten resin is transferred to a mixer, for example a rotary mixer with a studded rotor encased in a housing having a studded inner surface engaged with a stud on the rotor. Molten resin and volatile foam or blowing agent are fed to the inlet end of the mixer and discharged from the outlet end to the gel, with the flow generally in the axial direction. From the mixer, the gel is passed through a cooler and then the cooled gel is passed through a die which extrudes a generally rectangular plate. Non-limiting examples of procedures suitable for forming extruded polystyrene foams suitable for use in the present invention include US Pat. No. 5,011,866, all of which is incorporated herein by reference in its entirety; 3,704,083; And 5,011,866. Other examples of suitable processes include, but are not limited to, US Pat. Nos. 2,450,436, all of which are incorporated herein by reference; 2,669,751; 2,740,157; 2,740,157; 2,769,804; 2,769,804; 3,072,584; 3,072,584; And 3,215,647.

Any of a variety of known foaming agents, often referred to as blowing agents, can be used to make the extruded polystyrene foam of the present invention. Non-limiting examples of suitable foaming agents can be found in US Pat. No. 3,960,792, which is incorporated herein by reference in its entirety. In general, volatile carbon-containing chemicals are the broadest for this purpose. These include, for example, aliphatic hydrocarbons including ethane, ethylene, propane, propylene, butane, butylene, isobutane, pentane, neopentane, isopentane, hexane, heptane and mixtures thereof; Volatile halocarbons and / or halogenated hydrocarbons such as methyl chloride, chlorofluoromethane, bromochlorodifluoromethane, 1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane, Dichlorofluoromethane, dichlorodifluoromethane, chlorotrifluoromethane, trichlorofluoromethane, sym-tetrachlorodifluoroethane, 1,2,2-trichloro-1,1,2-trifluoro Ethane, sym-dichlorotetrafluoroethane; Volatile tetraalkylsilanes such as tetramethylsilane, ethyltrimethylsilane, isopropyltrimethylsilane, and n-propyltrimethylsilane; And mixtures of these materials. One preferred fluorine-containing blowing agent is 1,1-difluoroethane, also known as HFC-152a (FORMACEL Z-2, E. I. duPont de Nemours and Co.) because of its reported desirable ecological properties. Water-containing vegetable materials, such as finely divided corn sacks, may also be used as blowing agents. As described in US Pat. No. 4,559,367, such vegetable materials may also be used as fillers. Carbon dioxide may be used as a foaming agent, or at least one component of the foaming agent. Non-limiting examples of methods of using carbon dioxide as a blowing agent include, but are not limited to, US Pat. Nos. 5,006,566, all of which are incorporated herein by reference in their entirety; 5,189,071; 5,189,071; 5,189,072; 5,189,072; And 5,380,767. Non-limiting examples of other suitable blowing agents include nitrogen, argon and water, which include or do not include carbon dioxide. If desired, such blowing agents or blowing agent mixtures may be mixed with alcohols, hydrocarbons, or ethers of suitable volatiles, see for example US Pat. No. 6,420,442, which is incorporated herein by reference in its entirety.

Synergist

The flame retardant compositions of the present invention are suitable for use in most applications, but in some applications, further increases in their flame retardant efficiency may be required. In this regard, the flame retardant composition may optionally include any flame retardant synergist known in the art, such that when the flame retardant composition is used in a flame retardant polymer formulation, the flame retardant polymer formulation also includes an optional synergist. something to do. Non-limiting examples of suitable flame retardant synergists include (i) antimony compounds such as antimony trioxide, antimony tetraoxide, antimony pentoxide, and sodium antimonate; (ii) tin compounds, such as tin oxide and tin hydroxide; (iii) molybdenum compounds such as molybdenum oxide and ammonium molybdenum; (iv) zirconium compounds such as zirconium oxide and zirconium hydroxide; (v) boron compounds such as zinc borate and barium metaborate; (vi) dicumylperoxide; And (vii) dicumyl. Other components that can be used as flame retardant synergists include talc, hindered phenolic antioxidants, and light stabilizers. The ratio of the optional flame retardant synergist to the N-2,3-dibromopropyl-4,5-dibromohexahydrophthalimide component is conventional and can be varied to suit the needs of any given situation.

The ratio of the total amount of synergist to flame retardant I is typically in the range of about 1: 1 to about 1: 7. Preferably, synergists are used in ratios ranging from about 1: 2 to about 1: 4.

In a preferred embodiment, the flame retardant composition comprises an optional synergist. In a particularly preferred embodiment, the flame retardant composition comprises at least dicumyl as an optional synergist. In some embodiments, the flame retardant composition comprises only dicumyl as a synergist. The inventors have found that using dicumyl as a synergist, in particular in the presence of hydrotalcite, provides superior marginal oxygen index results compared to other combinations and other synergists alone. Without wishing to be bound by theory, the inventors have indicated that this is an unexpected synergistic effect, in particular an unexpected synergistic effect achieved using a combination of dicumyl and hydrotalcite, preferably synthetic hydrotalcite, more preferably DHT-4A. I think it is due to.

Generally, the synergist may be present in an amount ranging from about 0.01 to about 5 weight percent based on the weight of the flame retardant composition. Preferably, the synergist is present in an amount in the range of about 0.05 to about 3 weight percent on the same basis, and more preferably the synergist is present in an amount in the range of about 0.1 to about 1 weight percent on the same basis. In the most preferred embodiment, the synergist is present in an amount ranging from about 0.1 to about 0.5 weight percent on the same basis.

Other optional additive

Non-limiting examples of other additives suitable for use in the flame retardant polymer formulations and flame retardant compositions of the present invention include extrusion aids such as barium stearate or calcium stearate, organic peroxides, dyes, pigments, fillers, heat stabilizers, oxidation Preventive agents, antistatic agents, reinforcing agents, metal scavengers or inactivators, impact modifiers, processing aids, mold release aids, lubricants, antiblocking agents, other flame retardants, UV stabilizers, plasticizers, flow aids, etc. Included. If desired, nucleating agents such as calcium silicate or indigo may also be included in the flame retardant polymer formulation. The proportion of other optional additives is conventional and can be varied to suit the needs of any given situation.

The manner in which the various components of the flame retardant polymer formulation, both optional and otherwise, are formulated with polystyrene prior to extrusion is not critical to the present invention, and suitable techniques, methods or processes are known. For example, flame retardant compositions can be incorporated into extruded polystyrene-based foams by wet or dry techniques. Non-limiting examples of dry techniques include techniques for mixing a flame retardant composition with pellets of extruded polystyrene-based foams, and then extruding the mixture at elevated temperatures sufficient to melt the expanded polystyrene-based foams. Non-limiting examples of wet methods include mixing a solution of a flame retardant composition with the molten resin of an extruded polystyrene-based foam. Furthermore, flame retardant polymer formulations can be prepared using conventional blending equipment such as twin-screw extruders, Brabender mixers, or similar devices. It is also possible to separately add the individual components of the flame retardant polymer formulations of the invention to the extruded polystyrene-based foams. Preferably, however, the preformed flame retardant composition of the invention is blended with the extruded polystyrene foam.

The foregoing is directed to several embodiments of the present invention. Those skilled in the art will recognize that other means, which are equally effective, can be devised for carrying out the spirit of the invention. It should also be noted that the preferred embodiments of the present invention contemplate that all ranges discussed herein include ranges from slightly lesser amounts to slightly more amounts. For example, the amount of synergist may also include amounts ranging from about 0.5 to about 3 weight percent, from 0.05 to about 1 weight percent, from 3 to about 5 weight percent, and the like. The following examples illustrate the invention but are not intended to be limiting in any way.

Example 1

5 weight-% based on the weight of the FR, N-2,3-dibromopropyl-4,5-dibromohexahydrophthalimide, which is a flame retardant I referred to as "FR" in this example and the following examples Blended with various known thermal stability improvers in% or 10% by weight to form a flame retardant composition. Some of these flame retardant compositions were those according to the invention, such as EP-16, Zeolite A, and non-brominated epoxy oligomers, some of which were not according to the invention. The thermal stability of the flame retardant composition was then determined via dynamic thermogravimetric (“TGA”) analysis. The thermal stability of the flame retardant composition according to the invention was then compared with the thermal stability of the flame retardant composition not according to the invention. TGA measurement results are included in Table 1 below.

EP-16 as used herein refers to a brominated bisphenol-A epoxy resin sold by Dainippon Ink & Chemicals, Incorporated. DGETBBPA refers to diglycidyl ether of tetrabromobisphenol A and TSPP refers to tetra sodium polyphosphate. DBTM refers to dibutyl tin maleate and DHT 4A refers to the hydrotalcite marketed by Mipsui. Non-brominated epoxy oligomers (“non Br EO”) are sold under catalog number 40545-0 by Aldrich.

To perform the TGA test, approximately (10) μg of flame retardant composition was placed in a 70 μl alumina crucible without a lid. The crucible was placed in a 100% nitrogen atmosphere and the temperature of the crucible was raised in an increment of 10 ° C./min from the initial temperature of 30 ° C. until a final temperature of 750 ° C. was reached. As shown in Table 1, the temperatures at which the various flame retardant compositions lost their set weight percentages were measured and recorded.

As can be seen from Table 1, all flame retardant compositions containing DBTM and DHT 4A (hydrotalcite), which are well known heat stabilizers, unexpectedly do not show any thermal stability improvement over FR. However, flame retardant compositions containing DGETPPA, EP-16, TSPP, non-brominated epoxy oligomers, and Zeolite A show an improvement in thermal stability over FR.

Example 2

In this example, to test the effect of varying levels of hydrotalcite and halogenated aromatic epoxy oligomers on the TGA analysis of the flame retardant composition according to the invention, as illustrated in Table 2 below, FR was added at 2.5% by weight or 5%. Blended with weight percent halogenated aromatic epoxy oligomer (EP-16) and 2.5 weight percent or 5 weight percent hydrotalcite (DHT-4A), wherein all weight percents were based on the weight of FR.

To perform the TGA test, approximately (10) μg of flame retardant composition was placed in a 70 μl alumina crucible without a lid. The crucible was placed in a 100% nitrogen atmosphere and the temperature of the crucible was raised in an increment of 10 ° C./min from the initial temperature of 30 ° C. until a final temperature of 750 ° C. was reached. As shown in Table 1, the temperatures at which the various flame retardant compositions lost their set weight percentages were measured and recorded.

As can be seen in Table 2, 5% by weight of halogenated aromatic epoxy oligomers and 5% by weight of hydrotalcite provide flame retardant compositions with improved thermal stability compared to FR alone. However, the inventors surprisingly found that lower levels, i.e., 2.5% by weight of halogenated aromatic epoxy oligomers and hydrotalcites, compared to FR alone and also flame retardant compositions comprising 5% by weight of halogenated aromatic epoxy oligomers and hydrotalcites. It has been found to provide flame retardant compositions with improved thermal stability.

Example 3

The flame retardancy of the various flame retardant polymer formulations according to the invention was then analyzed. The flame retardancy of the flame retardant polymer formulation was determined according to its limit oxygen index ("LOI") measured according to ASTM D2863. The LOI value gives the oxygen concentration of the oxygen / nitrogen mixture that only barely sustains combustion of the material. The higher the LOI value, the better the flame retardant ability of the flame retardant polymer formulation.

The contents of the various flame retardant polymer formulations tested are shown in Tables 2 and 3 below along with the LOIs of the flame retardant polymer formulations. This flame retardant polymer formulation was formed by combining the flame retardant composition of Example 1 with a styrenic polymer obtained from Dow Chemical Corporation, a styrene-based polymer commonly used in polystyrene foam applications, and marketed under the name Styron 678E.

In addition, as a comparative flame retardant polymer formulation, HP900, a flame retardant composition commercially available from Albemarle Corporation, was blended with Styron 678E and also with 5% by weight TSPP and Styron 678E.

As can be seen from Table 2, Table 3, and the figures, when the flame retardant polymer formulation contains FR with EP-16, Zeolite A, or a non-brominated epoxy oligomer (flame retardant composition according to the invention) flame retardant polymer formulation The flame retardancy of water is improved. In addition, as illustrated in Table 1, the thermal stability of the flame retardant composition is also improved.

TSPP is a known thermal stability / flame retardant improver. For example, when the flame retardant polymer formulation contains HP900 and 5 wt% TSPP as the flame retardant composition, the flame retardancy is improved compared to the flame retardant polymer formulation containing only Styron 678E and HP900. However, very unexpectedly, when the flame retardant polymer formulation contains a flame retardant composition containing TSPP and FR, the FR-containing flame retardant polymer formulation demonstrates lower flame retardancy than the FR alone formulation, i.e. Has an antagonistic effect on However, as shown in Table 1, flame retardant compositions containing TSPP and FR demonstrate an improvement in thermal stability. Thus, to illustrate this, it is unexpected that only certain known heat stabilizers / flame retardants are suitable for improving both the flame retardancy and the thermal stability of the FR.

DHT 4A (hydrotalcite) is also a known thermal stability / flame retardant improver. Thus, while flame retardant polymer formulations containing FR / DHT 4A (hydrotalcite) flame retardant compositions demonstrate an improvement in flame retardancy, it is unexpected that the flame retardant compositions exhibit reduced thermal stability as shown in Table 1. To illustrate this again, it is unexpected that only certain known heat stabilizers / flame retardant improvers are suitable for improving both the flame retardancy and the thermal stability of the FR.

Accordingly, the inventors have found that only certain materials commonly used as flame retardant / heat stabilizer modifiers improve the thermal stability of flame retardant polymer formulations containing flame retardant compositions while at the same time N-2,3-dibromopropyl-4,5 It has been found that it can be used to improve all of the thermal stability of flame retardant compounds containing dibromohexahydrophthalimide flame retardant. In addition, the inventors unexpectedly find that some of the more commonly used flame retardant / heat stabilizer modifiers such as hydrotalcite (DHT 4A) or TSPP do not provide this benefit, and in some cases the desired properties, namely thermal stability and / or Or it is harmful to flame retardancy.

Example 4

In this example, the effects of varying concentrations of hydrotalcite, dicumyl, and combinations of these on the flame retardancy of various flame retardant polymer formulations according to the present invention were analyzed. The flame retardancy of the flame retardant polymer formulation was again determined according to its limit oxygen index ("LOI") measured according to ASTM D2863.

The contents of the various flame retardant polymer formulations tested are shown in Table 5 below along with the LOIs of such flame retardant polymer formulations. Such flame retardant polymer formulations include styrene-based polymers obtained from Dow Chemical Corporation, a styrene-based polymer commonly used in polystyrene foam applications, and sold under the name Styron 680, sold by Peroxid Chemie GMBH. 2,3-dimethyl, 2,3-diphenyl butane CAS # 1889-67-4) and the commercial name for CCDFB dicumyl and hydrotalcite, DHT-4A.

It should be noted that all component amounts in Table 5 are expressed in weight percent based on the total weight of the flame retardant polymer formulation.

As demonstrated in Table 5, as the amount of hydrotalcite in the flame retardant polymer formulation increases, the LOI of the flame retardant polymer formulation begins to increase, but then decreases. In fact, when the level increases above 0.3% by weight, the LOI of the flame retardant polymer formulation is actually worse than that of the flame retardant polymer formulation containing FR alone. Thus, the inventors have found that a preferred amount of hydrotalcite is present.

Furthermore, the inventors have found that the combination of hydrotalcite and dicumyl provides a LOI improvement over FR alone and also compared to flame retardant polymer formulations containing the same amount of hydrotalcite. We believe that this improvement is due to the synergistic effect between hydrotalcite and dicumyl.

Claims (55)

Flame retardant compositions having enhanced thermal stability and flame retardant efficiency in extruded polystyrene foam, comprising: a) flame retardant I in the range of about 60% to about 95% by weight based on the flame retardant composition; b) from about 1% to about 40% by weight based on the flame retardant composition, i) natural zeolite, ii) synthetic zeolite, iii) halogenated aromatic epoxide, iv) halogenated epoxy oligomer, v) non-halogenated epoxy oligomer, vi) hydrotalcite and vii) component (A) selected from the mixture of i) -vi); And Randomly, c) (i) antimony compounds; (ii) tin compounds; (iii) molybdenum compounds; (iv) zirconium compounds; (v) boron compounds; (vi) hydrotalcites; (vi) talc; (vii) dicumylperoxide; (viii) dicumyl; (ix) hindered phenolic antioxidants; (x) light stabilizers; And xi) a synergist selected from a mixture of i) -x) . The flame retardant composition according to claim 1, wherein component (A) is an epoxy compound selected from halogenated aromatic epoxides represented by the following general formula (I):

[Wherein X independently represents a chlorine or bromine atom, i and j each represent an integer of 1 to 4; n represents an average degree of polymerization in the range of 0.01 to 100; And T ₁ and T ₂ are independently selected from:

Wherein Ph represents a substituted or unsubstituted halogenated phenyl group, wherein the ring is substituted with one or more chlorine or bromine atoms}. 3. The halogenated aromatic epoxide of claim 2, wherein the halogenated aromatic epoxide is selected from diglycidyl ethers of halogenated bisphenol-A, wherein about 2 to about 4 halogen atoms are substituted on the bisphenol-A moiety, and the halogen atoms are chlorine, bromine, And flame retardant compositions thereof. The flame retardant composition of claim 3 wherein the halogen atoms are substantially all bromine atoms. The flame retardant composition of claim 1 wherein component (A) is an epoxy compound selected from halogenated epoxy oligomers. The flame retardant composition of claim 5 wherein the halogenated epoxy oligomer is at least one of the following: a) brominated bisphenol-A epoxy resin represented by the following general formula (II):

[Wherein n represents an average degree of polymerization in the range of 0.5 to 100] b) halogenated epoxy oligomers represented by formula (III)

[Wherein n represents an average degree of polymerization in the range of 0.5 to 100] c) halogenated epoxy oligomers represented by formula (IV):

[Wherein n represents an average degree of polymerization in the range of 0.5 to 100] d) Brominated bisphenol-A epoxy resins having a blocking agent at one end and represented by the following general formula (V):

[Wherein n represents an average degree of polymerization in the range of 0.5 to 100] e) brominated bisphenol-A epoxy resins having a blocking agent at one end and represented by the following general formula (VI):

[Wherein n represents an average degree of polymerization in the range of 0.5 to 100]. The method of claim 2 or 6, wherein (i) the antimony compound is selected from antimony trioxide, antimony tetraoxide, antimony pentoxide, and sodium antimonate; (ii) the tin compound is selected from tin oxide and tin hydroxide; (iii) the molybdenum compound is selected from molybdenum oxide and ammonium molybdenum; (iv) the zirconium compound is selected from zirconium oxide and zirconium hydroxide; And (v) the flame retardant composition wherein the boron compound is selected from zinc borate and barium metaborate. The flame retardant composition of claim 1 wherein component (A) is a natural or synthetic zeolite. The flame retardant composition of claim 1 wherein component (A) is a non-halogenated epoxy oligomer. 9. Flame retardant composition according to claim 8, wherein said synthetic zeolite is selected from Zeoline and Zeolite A. 10. A flame retardant composition according to claim 9, wherein said non-halogenated epoxy oligomer is selected from those having formulas (I) to (VI), wherein Br atoms of formulas (I) to (VI) are replaced with hydrogen atoms. 7. Flame retardant composition according to any one of claims 1, 2 or 6 comprising said synergist. The flame retardant composition of claim 12 wherein the synergist is dicumyl. The flame retardant composition of claim 1 wherein component A is selected from a) hydrotalcites, b) brominated bisphenol-A epoxy resins represented by formula (II), and c) mixtures thereof. The flame retardant composition of claim 13 wherein component A is selected from a) hydrotalcites, b) brominated bisphenol-A epoxy resins represented by formula (II), and c) mixtures thereof. The flame retardant composition of claim 12 wherein the synergist is present in an amount ranging from about 0.01 to about 5 weight percent based on the weight of the flame retardant composition. The flame retardant composition of claim 13 wherein the synergist is present in an amount ranging from about 0.1 to about 0.5 weight percent based on the weight of the flame retardant composition. The flame retardant composition of claim 16 wherein the ratio of the total amount of synergist to flame retardant I ranges from about 1: 1 to about 1: 7. The flame retardant composition of claim 17 wherein the ratio of the total amount of synergist to flame retardant I ranges from about 1: 2 to about 1: 4. The flame retardant composition of claim 12, wherein component A is present in an amount ranging from about 1 to about 25 weight percent based on the weight of the flame retardant composition. The flame retardant composition of claim 12, wherein component A is present in an amount ranging from about 1 to about 15 weight percent based on the weight of the flame retardant composition. The flame retardant composition of claim 17, wherein component A is a hydrotalcite and component A is present in an amount ranging from about 2 to about 6 weight percent based on the weight of the flame retardant composition. Flame retardant polymer formulations comprising: a) greater than about 50 weight percent extruded polystyrene foam based on the weight of the flame retardant polymer formulation; And b) flame retardant amount of the flame retardant composition comprising: i) N-2,3-dibromopropyl-4,5-dibromohexahydrophthalimide in the range of about 60% to about 95% by weight based on the flame retardant composition; ii) about 1% to about 40% by weight based on the flame retardant composition, i) natural zeolite, ii) synthetic zeolite, iii) halogenated aromatic epoxide, iv) halogenated epoxy oligomer, v) non-halogenated epoxy oligomer, vi ) Component (A) selected from a hydrotalcite and a mixture of vii) i) -vi); And Randomly, iii) (i) antimony compounds; (ii) tin compounds; (iii) molybdenum compounds; (iv) zirconium compounds; (v) boron compounds; (vi) hydrotalcites; (vi) talc; (vii) dicumylperoxide; (viii) dicumyl; (ix) hindered phenolic antioxidants; (x) light stabilizers; And xi) a synergist selected from a mixture of i) -x) . The flame retardant polymer formulation of claim 23 comprising more than about 75% by weight of extruded polystyrene foam, based on the weight of the flame retardant polymer formulation. The flame retardant polymer formulation of claim 23 comprising from about 90% to about 99.5% by weight of extruded polystyrene foam, based on the weight of the flame retardant polymer formulation. 24. The method of claim 23 wherein the amount of flame retardancy (for EPS and XPS) can achieve a DIN 4102 test of B2 or greater or a UL 94 test grade of V-2 or greater with a 1 / 8-inch thick specimen for 10 mm thick specimens. A flame retardant polymer formulation that is an amount of a flame retardant composition sufficient to provide a test specimen of the flame retardant polymer formulation. The flame retardant polymer formulation of claim 23, wherein the amount of flame retardant is necessary to provide a total halogen content of the flame retardant polymer formulation in the range of about 0.3 to about 10 weight percent based on the weight of the flame retardant polymer formulation. The flame retardant polymer formulation of claim 23, wherein the flame retardant amount ranges from about 0.01% to about 50% by weight based on the weight of the flame retardant polymer formulation. The flame retardant polymer formulation of claim 24, wherein the amount of flame retardant is in a range from about 0.01 wt% to about 25 wt%, based on the weight of the flame retardant polymer formulation. The flame retardant polymer formulation of claim 24, wherein the amount of flame retardant is from about 0.5% to about 7% by weight based on the weight of the flame retardant polymer formulation. The method of claim 23 further comprising: extrusion aids such as barium stearate or calcium stearate, organic peroxides, dyes, pigments, fillers, heat stabilizers, antioxidants, antistatic agents, reinforcing agents, metal scavengers or inactivating agents, Flame retardant polymer formulations including impact modifiers, processing aids, release aids, lubricants, antiblocking agents, other flame retardants, UV stabilizers, plasticizers, flow aids, nucleating agents such as calcium silicate or indigo, and the like. 31. A flame retardant polymer formulation as claimed in claim 30 wherein component (A) of said flame retardant composition is an epoxy compound selected from halogenated aromatic epoxides represented by formula (I):

[Wherein X independently represents a chlorine or bromine atom, i and j each represent an integer of 1 to 4; n represents an average degree of polymerization in the range of 0.01 to 100; And T ₁ and T ₂ are independently selected from:

Wherein Ph represents a substituted or unsubstituted halogenated phenyl group, wherein the ring is substituted with one or more chlorine or bromine atoms}. 33. The halogenated aromatic epoxide of claim 32 wherein the halogenated aromatic epoxide is selected from diglycidyl ethers of halogenated bisphenol-A, wherein from about 2 to about 4 halogen atoms are substituted on the bisphenol-A moiety and the halogen atoms are chlorine, bromine And flame retardant polymer formulations thereof. The flame retardant polymer formulation of claim 23, wherein component (A) is an epoxy compound selected from halogenated epoxy oligomers, wherein the halogenated epoxy oligomer is selected from one or more of: a) brominated bisphenol-A epoxy resin represented by the following general formula (II):

[Wherein n represents an average degree of polymerization in the range of 0.5 to 100] b) halogenated epoxy oligomers represented by formula (III)

[Wherein n represents an average degree of polymerization in the range of 0.5 to 100] c) halogenated epoxy oligomers represented by formula (IV):

[Wherein n represents an average degree of polymerization in the range of 0.5 to 100] d) Brominated bisphenol-A epoxy resins having a blocking agent at one end and represented by the following general formula (V):

[Wherein n represents an average degree of polymerization in the range of 0.5 to 100] e) brominated bisphenol-A epoxy resins having a blocking agent at one end and represented by the following general formula (VI):

[Wherein n represents an average degree of polymerization in the range of 0.5 to 100]. A flame retardant polymer formulation as claimed in claim 23 wherein component (A) is a natural or synthetic zeolite or non-halogenated epoxy oligomer. The flame retardant polymer formulation of claim 34, wherein said non-halogenated epoxy oligomer is selected from those having formulas (I) to (VI), wherein Br atoms of formulas (I) to (VI) are replaced with hydrogen atoms. . 35. A flame retardant polymer formulation as claimed in any of claims 23, 32 or 34 wherein said flame retardant composition comprises said synergist. 38. The flame retardant composition of claim 37 wherein said synergist is dicumyl. 38. The composition of claim 37 wherein component A is selected from a) hydrotalcites, b) brominated bisphenol-A epoxy resins represented by formula (II), and c) mixtures thereof, wherein component A is used to determine the weight of the flame retardant composition Flame retardant composition present in an amount in the range of about 1 to about 25% by weight. 39. The component of claim 38 wherein component A is selected from a) a hydrotalcite, b) a brominated bisphenol-A epoxy resin represented by formula (II), and c) mixtures thereof, wherein component A is the weight of the flame retardant composition A flame retardant composition present in an amount in the range of from about 1 to about 15% by weight, based on the total weight of the composition. 38. The flame retardant composition of claim 37, wherein said synergist is present in an amount in the range of from about 0.01 to about 5 weight percent based on the weight of the flame retardant composition I. The flame retardant composition of claim 40 wherein the synergist is present in an amount ranging from about 0.1 to about 0.5 weight percent based on the weight of the flame retardant composition. 38. The flame retardant composition of claim 37, wherein component A is a hydrotalcite and component A is present in an amount ranging from about 2 to about 6 weight percent based on the weight of the flame retardant composition. The flame retardant composition of claim 38, wherein component A is a hydrotalcite and component A is present in an amount in the range of about 2 to about 6 weight percent based on the weight of the flame retardant composition. A process for producing a molded flame retardant extruded polystyrene product comprising blending polystyrene, a blowing agent, and a flame retardant composition according to the present invention to form a blended product and extruding the blended product through a die, wherein the flame retardant composition comprises Process Including: a) N-2,3-dibromopropyl-4,5-dibromohexahydrophthalimide in the range of about 60% to about 95% by weight based on the flame retardant composition; And b) from about 1% to about 40% by weight based on the flame retardant composition, i) natural zeolite, ii) synthetic zeolite, iii) halogenated aromatic epoxide, iv) halogenated epoxy oligomer, v) non-halogenated epoxy oligomer, vi) hydrotalcite and vii) component (A) selected from the mixture of i) -vi); And Randomly, c) (i) antimony compounds; (ii) tin compounds; (iii) molybdenum compounds; (iv) zirconium compounds; (v) boron compounds; (vi) hydrotalcites; (vi) talc; (vii) dicumylperoxide; (viii) dicumyl; (ix) hindered phenolic antioxidants; (x) light stabilizers; And xi) a synergist selected from a mixture of i) -x) . 46. An extrusion aid, such as barium stearate or calcium stearate, an organic peroxide, dye, pigment, filler, heat stabilizer, antioxidant, antistatic agent, reinforcing agent, metal scavenger or inactivating agent, impact modifier. Processing aids, release aids, lubricants, antiblocking agents, other flame retardants, UV stabilizers, plasticizers, flow aids, nucleating agents such as calcium silicates or indigo, and the like, which are further used in the preparation of the blended product. 46. The process of claim 45, wherein component (A) of the flame retardant composition is an epoxy compound selected from halogenated aromatic epoxides represented by formula (I):

[Wherein X independently represents a chlorine or bromine atom, i and j each represent an integer of 1 to 4; n represents an average degree of polymerization in the range of 0.01 to 100; And T ₁ and T ₂ are independently selected from:

Wherein Ph represents a substituted or unsubstituted halogenated phenyl group, wherein the ring is substituted with one or more chlorine or bromine atoms}. 48. The halogenated aromatic epoxide of claim 47 wherein the halogenated aromatic epoxide is selected from diglycidyl ethers of halogenated bisphenol-A, wherein from about 2 to about 4 halogen atoms are substituted on the bisphenol-A moiety and the halogen atoms are chlorine, bromine , And mixtures thereof. 46. The process of claim 45, wherein component (A) is an epoxy compound selected from halogenated epoxy oligomers, wherein said halogenated epoxy oligomer is selected from one or more of: a) brominated bisphenol-A epoxy resin represented by the following general formula (II):

[Wherein n represents an average degree of polymerization in the range of 0.5 to 100] b) halogenated epoxy oligomers represented by formula (III)

[Wherein n represents an average degree of polymerization in the range of 0.5 to 100] c) halogenated epoxy oligomers represented by formula (IV):

[Wherein n represents an average degree of polymerization in the range of 0.5 to 100] d) Brominated bisphenol-A epoxy resins having a blocking agent at one end and represented by the following general formula (V):

[Wherein n represents an average degree of polymerization in the range of 0.5 to 100] e) brominated bisphenol-A epoxy resins having a blocking agent at one end and represented by the following general formula (VI):

[Wherein n represents an average degree of polymerization in the range of 0.5 to 100]. 46. The process of claim 45, wherein component (A) is a natural or synthetic zeolite or non-halogenated epoxy oligomer. 50. The process of claim 49, wherein said non-halogenated epoxy oligomer is selected from those having formulas (I) to (VI), wherein Br atoms of formulas (I) to (VI) are replaced with hydrogen atoms. 50. The process according to any one of claims 45, 47 or 49, wherein said flame retardant composition comprises said synergist. 53. The process of claim 52, wherein said synergist is dicumyl. 53. The component of claim 52 wherein component A is selected from a) a hydrotalcite, b) a brominated bisphenol-A epoxy resin represented by formula (II), and c) mixtures thereof, wherein component A is about based on the weight of the flame retardant Present in an amount ranging from 1 to about 25% by weight. 55. The component of claim 53 wherein component A is selected from a) a hydrotalcite, b) a brominated bisphenol-A epoxy resin represented by formula (II), and c) a mixture thereof, wherein component A is based on the weight of the flame retardant Present in an amount ranging from about 1 to about 15 weight percent.